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WO1999045048A1 - Ionomeres sensiblement fluores - Google Patents

Ionomeres sensiblement fluores Download PDF

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Publication number
WO1999045048A1
WO1999045048A1 PCT/US1999/004574 US9904574W WO9945048A1 WO 1999045048 A1 WO1999045048 A1 WO 1999045048A1 US 9904574 W US9904574 W US 9904574W WO 9945048 A1 WO9945048 A1 WO 9945048A1
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WIPO (PCT)
Prior art keywords
group
ionomer
optionally substituted
liquid
ocf
Prior art date
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PCT/US1999/004574
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English (en)
Inventor
Andrew Edward Feiring
Christopher Marc Doyle
Mark Gerrit Roelofs
William Brown Farnham
Paul Gregory Bekiarian
Hanne A. K. Blau
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to AU29781/99A priority Critical patent/AU2978199A/en
Priority to DE69904919T priority patent/DE69904919T2/de
Priority to CA002321695A priority patent/CA2321695A1/fr
Priority to EP99911046A priority patent/EP1060200B1/fr
Priority to AT99911046T priority patent/ATE231169T1/de
Priority to IL13793299A priority patent/IL137932A0/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to JP2000534589A priority patent/JP4417554B2/ja
Priority to KR1020007009720A priority patent/KR20010041541A/ko
Publication of WO1999045048A1 publication Critical patent/WO1999045048A1/fr
Priority to NO20004334A priority patent/NO20004334L/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers

Definitions

  • VF2 with vinyl ethoxy sulfonyl fluorides containing one ether linkage.
  • TFE tetrafluoroethylene
  • Connolly et al. U.S. 3,282,875 disclose the terpolymer of VF2 with perfluorosulfonyl fluoride ethoxy propyl vinyl ether (PSEPVE) and hexafluoropropylene (HFP). They broadly teach an emulsion polymerization process said to be applicable to copolymerization of vinyl ethers with any ethylenically unsaturated comonomer, with greatest applicability to fluorinated monomers.
  • DesMarteau U.S. 5,463,005
  • DesMarteau are copolymers formed by aqueous emulsion polymerization of the sodium salt form of (I) with tetrafluoroethylene. Further disclosed are compositions consisting of the acid-form of the imide copolymer of DesMarteau in combination with dimethylformamide (hereinafter DMF) to provide a conductive composition.
  • DMF dimethylformamide
  • Armand U. S. 4,818,644 discloses metal salts based on anions having the structure R -SO 2 CR-SO 2 R'f where R f and R'f are perfluorinated groups having from 1 to 10 carbon atoms and R is a hydrogen or an alkyl group having from 1 to 30 carbon atoms.
  • the lithium salts of these compounds are useful in combination with organic solvents or macromolecular solvents for making electrolyte solutions for lithium batteries.
  • Armand et al. further disclose (EP 0 850 921) salts and ionomeric polymers derived from malononitrile Z-C(CN)2 where Z represents an electron-withdrawing group and Z can also contain a polymerizable function. Ionomers based on these compounds are disclosed having styrenic or vinyl functional groups for polymerization. Copolymers of these monomers with substantially fluorinated monomers such as VF2 are not disclosed.
  • CF 2 CF-OCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 NMSO 2 Rf and copolymers thereof with tetrafluoroethylene.
  • the present invention provides for an ionic polymer (ionomer) comprising monomer units of VF2 and further comprising 2-50 mol-% of monomer units having pendant groups comprising the radical represented by the formula
  • M + is H + or a univalent metal cation
  • R 3 is an alkyl group of 1-6 carbons optionally substituted with one or more ether oxygens, or an aryl group optionally further substituted;
  • the present invention further provides for an ethylenically unsaturated composition represented by the formula
  • CF 2 CF(OCF 2 CFR) a OCF 2 (CFR') b SO 2 C-(M + )(Y)(Z) (II)
  • Y and Z are electron-withdrawing groups selected from the group consisting of CN, SO 2 R , P(O)(OR 3 ) 2 , CO 2 R 3 , P(O)R3 2 , C(O)R f C(O)R3, and cycloalkenyl groups formed therewith wherein Rf is a perfluoroalkyl group of 1-10 carbons optionally substituted with one or more ether oxygens; R3 is an alkyl group of 1-6 carbons optionally substituted with one or more ether oxygens, or an aryl group optionally further substituted;
  • Y and Z are the same or different.
  • the present invention further provides a method for making a methide ionomer the method comprising, combining in an inert organic liquid at a temperature in the range of 0-150°C a copolymer comprising monomer units of VF2 and 2-50 mol-% of monomer units represented by the formula:
  • the present invention further provides a method for making a methide composition the method comprising, combining an inert organic solvent at a temperature in the range of 0-100°C a composition represented by the formula
  • A is Br or Cl
  • the present invention further provides a process for forming an ionomer, the process comprising combining in an aqueous reaction medium VF2 with an ionic monomer represented by the formula
  • CF 2 CF-(OCF 2 CFR) a OCF 2 (CFR SO 2 X-(M + )(Y)(Z) c (II)
  • M + is H + or a univalent metal cation
  • the present invention further provides for an ionically conductive composition comprising the polymer of the invention and a liquid imibibed therewithin.
  • the present invention further provides for an electrode comprising at least one electrode active material, the ionomeric polymer of the present invention mixed therewith, and a liquid imbibed therewithin.
  • the present invention further comprises an electrochemical cell comprising a positive electrode, a negative electrode, a separator disposed between the positive and negative electrodes, and a means for connecting the cell to an outside load or source wherein at least one of the group consisting of the separator, the cathode, and the anode, comprises the ionically conductive composition of the invention.
  • sulfonyl methide refers to a functional group wherein an ionically bonded carbon atom is also bonded to at least one fluoroalkylsulfonyl group
  • sulfonyl imide refers to a functional group wherein an ionically bonded nitrogen atom is also bonded to at least one fmoroalkylsulfonyl group.
  • the conductive compositions of the present invention are readily melt processible into electrodes and separators useful in assembling batteries in low cost continuous or semi-continuous manufacturing processes. No previous ionomer based composition suitable for use in electrochemical cells is known to exhibit melt processibility.
  • the ionomers of the present invention comprise monomer units derived from VF2 and 2-50 mol-%, preferably 2-20 mol-%, most preferably 3-12 mol-%, of ionic monomer units having pendant groups comprising the radical represented by the formula
  • R 3 is an alkyl group of 1-6 carbons optionally substituted with one or more ether oxygens, or an aryl group optionally further substituted;
  • a 0 or 1
  • R CF 3
  • R F
  • b 1
  • X is C
  • Y and Z are CN or CO 2 R 3 where R 3 is C 2 H 5
  • Y is preferably SO 2 R f where Rf is CF3 or C 2 F5
  • M + is H + or alkali metal cation.
  • M + is a lithium cation.
  • the ionomer of the invention exhibits a melting point of 150°C or higher as determined by the peak of the endotherm as measured by differential scanning calorimetry (ASTMD4591).
  • the methide ionomers of the present invention may be formed by copolymerization of (II) with VF2 according to the teachings of Connolly, op.cit..
  • the methide ionomer is made by the process of the invention, wherein in a preparatory step is formed a copolymer of VF2 with the sulfonyl fluoride monomer (III).
  • the polymerization of (III) with VF2 may be conducted according to the teachings of Connolly et al, op.cit.
  • the polymerization is conducted with pre-emulsified liquid comonomer in a reaction mixture as taught hereinbelow.
  • the ionomers formed from non-ionic polymer which has been polymerized in such fashion exhibit surprisingly high melting points of ca. 150°C or higher as determined from the peak of the endotherm in differential scanning calorimetry (ASTM D4591) in view of their bulk comonomer contents.
  • the non-ionic sulfonyl fluoride copolymer is then contacted in an inert organic liquid at a temperature of 0-150°C, preferably 20-70°C, with a carbanion derived from CH 2 YZ, wherein Y and Z are electron- withdrawing groups selected from the group consisting of CN, SO 2 R f , SO 2 R 3 , P(O)(OR 3 ) 2 , CO 2 R 3 , P(O)R 3 2 , C(O)R f C(O)R 3 , and cycloalkenyl groups formed therewith wherein Rf is a perfluoroalkyl group of 1-10 carbons optionally substitued with one or more ether oxygens; R 3 is an alkyl group of 1-6 carbons optionally substituted with one or more ether oxygens, or an aryl group optionally further substituted; Y and Z are the same or different.
  • Y and Z are CN or CO R 3 where R 3 is C 2 H 5
  • the base used to generate reactive species from CH 2 YZ is preferably an alkali metal hydride, most preferably lithium hydride.
  • the combination is allowed to react until the sulfonyl fluoride is completely converted, which takes typically 15-20 hours in the preferred temperature range of 20-70°C.
  • CH YZ as hereinabove described is combined with the copolymer of VF2 and (III), and lithium hydride in the inert organic liquid in the ratio of one gram equivalent weight of CH 2 YZ and two gram equivalent weights of lithium hydride per gram equivalent weight of sulfonyl fluoride.
  • Suitable inert organic liquids include oxygen-containing solvents such as dialkyl ethers, dimethoxyethane, tetrahydrofuran, dioxane, sulfolane, dimethyl sulfoxide, n-methyl pyrrolidone, dimethyl formamide, and acetonitrile.
  • oxygen-containing solvents such as dialkyl ethers, dimethoxyethane, tetrahydrofuran, dioxane, sulfolane, dimethyl sulfoxide, n-methyl pyrrolidone, dimethyl formamide, and acetonitrile.
  • the preferred solvent will also be readily removed upon completion of the reaction.
  • Preferred is dimethoxyethane.
  • the metal fluoride coproduct formed in the methidization process of the invention may be removed, if desired, by extraction or a dialysis process using water.
  • the liquid medium in which the ionic species is formed often forms highly stable solvates therewith, making it difficult to fully remove that liquid by ordinary means such as drying or distillation.
  • the residual liquid is preferably removed by addition of another metal ion ligating agent such as an organic carbonate, sulfolane, alkylphosphate, or dimethoxyethane which replaces the residual liquid, typically at moderately elevated temperatures in an anhydrous fluid such as toluene.
  • a monomeric form of the methide moiety of the ionomer of the invention may be formed by starting with the unsaturated olefinic structure (III), followed by bromination as is known in the art in order to protect the double bond, reaction as hereinabove described for the analogous copolymer, followed by treatment with Zn powder to yield the polymerizable double bond.
  • VF2 is copolymerized with the monomeric composition represented by
  • CF 2 CF(OCF 2 CFR) a OCF 2 (CFR') b SO 2 N(M + )SO 2 R f ' (V)
  • a 0 or 1
  • R CF 3
  • R' F
  • b 1
  • M + is an alkali metal cation, most preferably lithium cation.
  • the olefinic monomer (V) may be synthesized according to the teachings of Xue, op.cit.
  • the polymerization may be effected according to the teachings of Connolly et al, op.cit. It is found in the practice of the present invention that the method by which the ionomer is formed can have a large effect on the melting temperature of the ionomer formed thereby. Melting point is of importance because a higher melting ionomer will provide a higher use temperature in such applications as lithium batteries.
  • the prior art teaches an aqueous emulsion process for copolymerizing methide or imide monomers according to DesMarteau or Xue, op.cit,, with tetrafluoroethylene (TFE). Reaction kinetics dictate that the process of
  • DesMarteau necessarily will result in limited, nearly random incorporation of the imide or methide monomers.
  • the rate of incorporation and distribution of a comonomer in copolymerization with VF2 depends upon the availability of the comonomer in the aqueous polymerization medium. It has been found very surprisingly than when the methide and imide ionomers herein are copolymerized with VF2 in the aqueous emulsion polymerization of the art such as in Connolly et al, op.cit., ionically rich and ionically poor regions are developed. This results in an ionomer exhibiting a melting temperature higher than that achieved when an ionomer of the same overall composition is formed by first copolymerizing VF2 with (III) using the same process followed by forming the ionomer.
  • An alternative means for providing the desired higher melting ionomer while avoiding the pitfalls of unwanted side reactions associated with polymerizing the ionic species, is to copolymerize VF2 with (III) in an aqueous medium wherein the liquid-liquid interface is substantially increased over that in the method of Connolly such as that in which the water, surfactant and monomer are pre-emulsified under very high shear mixing conditions as hereinbelow described.
  • CF 2 CF(OCF 2 CFR) a OCF 2 (CFR') b SO 2 F (III)
  • Suitable solvents include acetonitrile, dioxane, and sulfolane.
  • the mixture thus formed is heated to a temperature in the range of 50-150°C, preferably 70-90°C, and the reaction is allowed to proceed preferably until the Rf SO 2 NH 2 has been consumed as determined by NMR.
  • the product which remains in solution is separated by filtration.
  • the reaction product is then contacted with metallic zinc, preferably by slurrying Zn powder into the solution, at ambient temperature and then heated for several hours, as taught in U.S. Patent 5,463,005, preferably followed by filtering and washing with an anhydrous, aprotic organic solvent such as acetonitrile.
  • CF 2 CF(OCF 2 CFR) a OCF 2 (CFR') b SO 2 N(M)SO 2 R f * (V)
  • the lithiated imide form of structure (V) is then copolymerized with NF2 according to the teachings of Connolly et al. Unlike the methide embodiment, wherein it is preferred to first make a copolymer of VF2 and (II) followed by methidization, in the case of the imide it is highly preferred to first make the imidized monomer (V) followed by polymerization with VF2.
  • the ionomer is preferably formed into a film or sheet.
  • Films may be formed according to processes known in the art.
  • the ionomer is diluted with a solvent such as DMAC, the mixture cast onto a smooth surface such as a glass plate using a doctor knife or other device known in the art to assist in depositing films on a substrate, and the solvent evaporated.
  • a solvent such as DMAC
  • the ionomer of the invention is first combined with a plasticizer and then is formed into a film or sheet by a melt process.
  • the melt process is an extrusion process.
  • the ionomers of the present invention may exhibit a low level of ionic conductivity in the dry state, typically about 10" 7 S/cm at room temperature.
  • the ionomer may be combined with a liquid to achieve higher levels of ionic conductivity.
  • the ionomer will be in the acid form or the metal salt form, the particular metal being determined by the application as well.
  • the liquid employed therewith will likewise be dictated by the application.
  • Conductive compositions may thus be formed by combining together the ionomers of the present invention with solvents using a variety of techniques known in the art such as imbibing a dry ionomer film in a mixture of solvents or exposure of a dry film to a solvent vapor under controlled conditions or combining the ionomer with the solvents in a melt state and extruding films of controlled composition.
  • Preferred solvents include water, nonaqueous solvents such as linear and cyclic carbonates, alcohols, esters, lactones, ethers, sulfoxides, amides, sulfonamides, and sulfones, subject to the general considerations discussed above.
  • solvents combined with the ionomers of the present invention to form conductive compositions can optionally contain additional mobile salts which may be preferred for specific applications.
  • additional mobile salts which may be preferred for specific applications.
  • Other solvents suitable for forming conductive compositions include ionic liquids such as 1- methyl-3-butyl-imidazolium trifluoromethane sulfonate.
  • a variety of chemical agents can be added to these conductive compositions for purposes of improving ionic conductivity through the influence of the chemical agent on the dissociation or mobility of the ions within the
  • Such chemical agents include but are not limited to cationic complexing agents such as crown ethers and aza ethers and anion complexing agents such as BR 3 compounds where R is aryl, fluoro-substituted alkyl or aryl.
  • the ionomers of the present invention provide several unexpected benefits over the ionomers of the art. It is known in the art that VF2 polymers and copolymers exhibit electrochemical stability which makes them structural materials of choice for use in lithium batteries. Compared to the ionomers in the art which contain fluorosulfonate salts, the ionomers of the present invention comprise fluorosulfonylmethide or imide salts which exhibit higher dissociation in organic solvents thereby providing conductive compositions formed therefrom with surprisingly high conductivity.
  • the preferred conductive compositions of the present invention comprising the lithium salt embodiments of the ionomers of the invention and aprotic organic solvents, most preferably organic carbonates and lactones, are particularly well-suited for use in lithium batteries.
  • aprotic organic solvents most preferably organic carbonates and lactones
  • the higher affinity of the ionomers of the invention to organic solvents makes melt processing or casting of membranes a useful process for the production thereof; and, on the other hand, provides for higher uptake of the preferred organic carbonates in the preferred conductive compositions of the invention, leading to higher conductivities thereby.
  • compositions of an ionomer of the invention containing at least 50% VF2 more preferably at least 80% VF2 may become plasticized by the solvents imbibed within it, with concomitant decrease in mechanical strength of the membrane. In some applications, it may be desirable to enhance the properties of the solvent-swollen membrane.
  • Means available for improving the mechanical properties include: 1) incorporation into the polymer by means known in the art, a non-ionic third monomer that is not solvent sensitive; 2) formation by known means of a polymer blend with a non-ionic polymer that is less solvent sensitive; 3) blending by known means of the ionomer of the invention with an inert filler; 4) blending different compositions of ionic copolymers.
  • compositionally heterogeneous -SO 2 F-containing copolymer as precursor for the ionomeric form. Combined attributes of increased conductivity and enhanced mechanical strength are thereby obtained.
  • Preferred termonomers include tetrafluoroethylene, hexafluoropropylene, ethylene and the perfluoroalkylvinyl ethers. Termonomers are preferably present in the polymer at a concentration of up to 30 mol-%.
  • Polymers suitable for blending with ionomers of the invention include poly(tetrafluoroethylene) and copolymers thereof with hexafluoropropylene or perfluoroalkyl vinyl ethers, polyvinylidene fluoride homopolymer and a copolymer thereof with hexafluoropropylene, and polyethylene oxide.
  • a preferred composition comprises 25 to 50 weight % PVF2 homopolymer blended with the VF2 ionomer of the present invention. These materials are blended together by means common in the art such as mixing in a common diluent such as DMAC or propylene carbonate and then casting a membrane.
  • Suitable inert fillers include SiO 2 , Al O 3 , TiO 2 , or CaF 2 . High surface area particles less than 1.0 micron in diameter are desired, such as are available for the preferred grade of SiO 2 under the trade name Cab-o-sil® TS-530 silica. Loadings of up to 50 weight % filler are preferred.
  • the preferred electrode of the invention comprises a mixture of one or more electrode active materials in particulate form, the ionomer of the invention, at least one electron conductive additive, and at least one organic carbonate.
  • Examples of useful anode active materials include, but are not limited to, carbon (graphitic, coke-type, mesocarbon microbeads, carbon fibers, polyacenes, and the like) and lithium-intercalated carbon, lithium metal nitrides such as Li 6C00.4N, lithium metal, and lithium alloys, such as alloys of lithium with aluminum, tin, magnesium, mercury, manganese, iron, antimony, cadmium, and zinc, alloy forming anode compounds with inert metallic frameworks such as tin-iron-carbon or tin- manganese-carbon ternary compounds, metal oxides or lithium metal oxides such as tin oxide, iron oxide, titanium oxide, tantalum oxide, niobium oxide, or tungsten oxide, and electronically anion or cation-doping conductive polymers such as polyaniline.
  • Lithium intercalation anodes employing graphitic carbon such as MCMB 2528 from Osaka Gas Chemical Co. are preferred.
  • Useful cathode active materials include, but are not limited to, transition metal oxides such as spinel LiMn 2 O layered LiMnO 2 , LiNiO 2 , LiCoO 2 ,
  • LiNi x Co y O 2 iron oxides or lithiated iron oxides such as LiFeO 2 , or vanadium oxides such as LiV 2 O5, LiVgO ⁇ 3 , LiNiVO LiCoVO4, or the above compounds in nonstoichiometric, disordered, amorphous, or overlithiated or underlithiated
  • the above compounds doped with small amounts of other divalent or trivalent metallic cations such as Fe 2+ , Ti 2+ , Zn 2+ , Ni 2+ , Co 2+ , Cu + , C r 3 + , F e 3 + , AP + , Ni 3+ , Co3 + Mn 3+ , etc., sulfur compounds such as solid sulfur, organic disulfides, or metal sulfides such as TiS 2 or MoS 2 , electronically-conducting polymers such as polyaniline and its derivatives, polypyrrole derivatives, polyparaphenylene derivatives, polythiophene derivatives, or their copolymers, or mixtures of any of the above compounds.
  • other divalent or trivalent metallic cations such as Fe 2+ , Ti 2+ , Zn 2+ , Ni 2+ , Co 2+ , Cu + , C r 3 + , F e 3 + , AP + , Ni 3+ , Co3 + Mn 3+ , etc.
  • Particle size of the active material should range from about 1 to 100 microns.
  • Preferred are transition metal oxides such as LiMn 2 U4, LiNiO 2 , LiCoO 2 , and LiNi x Co y O 2 .
  • a highly preferred electron conductive aid is carbon black, preferably Super P carbon black, available from the MMM S.A. Carbon, Brussels, Belgium, in the concentration range of 1-10%.
  • the volume fraction of the lithium ionomer in the finished electrode is between 4 and 40%.
  • the electrode of the invention may conveniently be made by dispersion or dissolution of all polymeric components into a common solvent and mixing together with the electrode active particles the carbon black particles.
  • the preferred electrode active material is LiNi x C ⁇ _ x O wherein 0 ⁇ x ⁇ 1
  • the preferred electrode active material is graphitized mesocarbon microbeads.
  • a preferred lithium battery electrode of the invention can be fabricated by dispersing or dissolving ionomer of the invention in a mixture of propylene carbonate and cyclopentanone, followed by addition of particles of electrode active material and carbon black, followed by deposition of a film on a substrate and drying.
  • the components of the electrode are mixed together and fed to an extruder wherein they are mixed to form a homogeneous melt and extruded into a film.
  • the resultant preferred electrode will comprise electrode active material, conductive carbon black, and ionomer of the invention, where, preferably, the weight ratio of ionomer to electrode active material is between 0.05 and 0.8 and the weight ratio of carbon black to electrode active material is between 0.01 and 0.2. Most preferably the weight ratio of ionomer to electrode active material is between 0.1 and 0.25 and the weight ratio of carbon black to electrode active material is between 0.02 and 0.1.
  • This electrode can then be cast from solution onto a suitable support such as a glass plate, inert polymer carrier web, or current collector metal foil, and formed into a film using techniques well-known in the art. The electrode film thus produced can then be incorporated into a multi-layer electrochemical cell structure by lamination.
  • Battery solvents may be added to the battery component films individually or added to the battery laminated cells using a variety of techniques known in the
  • Preferred battery solvents for forming conductive compositions with the ionomeric polymers of the present invention suitable for usage in lithium batteries include dipolar aprotic liquids such as the linear and cyclic carbonates, esters, lactones, amides, sulfoxides, sulfones, sulfamides, and ethers.
  • Preferred solvents are mixtures of cyclic carbonates or lactones such as ethylene carbonate, propylene carbonate, butylene carbonates, vinylene carbonate, gamma-butyrolactone, fluoro or chloro-substituted cyclic carbonates with linear carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, and fluoro and chloro substituted linear carbonates.
  • ethylene carbonate, propylene carbonate, and gamma-butyrolactone with linear carbonates such as diethyl carbonate and/or ethyl methyl carbonate.
  • Most preferred are mixtures of ethylene carbonate with propylene carbonate in weight ratios of from 50:50 to 80:20 of ethylene carbonate to propylene carbonate.
  • a battery is formed from one or more electrochemical cells formed by laminating together in film form the anode, cathode, and separator compositions of the present invention, all of which have been rigorously dried prior to addition of a liquid selected from the group of organic carbonates and mixtures thereof, a mixture of ethylene carbonate and propylene carbonate being most preferred.
  • the individual film layers consisting of an anode, separator, and cathode are compounded individually in a melt state and extruded into film form using temperatures from 90 to 130°C.
  • These individual layers already containing the preferred battery solvents such as mixtures of ethylene carbonate and propylene carbonate are laminated together to form battery cells which do not require additional post-treatment such as drying or extraction steps.
  • additional polymers or solvents for such purposes as improving the binding of the components thereof, or providing improved structural integrity of an article fabricated therefrom.
  • additional material is PVF2 homopolymer, which may be incorporated simply by dissolving the polymer into the same solution from which the electrode is being formed or melt compounding the polymer into other components during mixing or extrusion, as hereinabove described.
  • CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 C(Li)(SO 2 CF 3 ) 2 .
  • This monomer (35.6 g, 0.05 mole) in 500 ml of deionized water is charged to a 1 -liter vertical stirred autoclave. The vessel is closed, twice pressured to 100 psi nitrogen and vented, cooled to about 5°C and evacuated. Vinylidene fluoride (50.0 g, 0.78 mol) is added, and the stirred (750 rpm) contents are heated to 60°C. A solution of potassium persulfate (0.08 g in 20 mL water) is added over a 10 minute interval. After about 8 hours, the remaining pressure is vented and the aqueous solution is
  • EXAMPLE 3 A copolymer of VF2 and PSEPVE was synthesized according to the following method. 150 g of PSEPVE liquid was suspended in aqueous emulsion by combining with a solution of 35 g of ammonium perfluorooctanoate in 600 ml of distilled water using a Microfluidics, Inc. microfluidizer. The suspension was then diluted to 1 liter total volume with additional distilled water. The suspension so formed was charged to a nitrogen purged 4 liter horizontal autoclave equipped with a mechanical agitator, along with an additional 1500 mL of distilled water.
  • the reactor was evacuated, then pressurized to 0 psig with vinylidene fluoride three times, then heated to 60°C, pressurized to 300 psig with vinylidene fluoride, and agitated at 200 rpm.
  • a solution of aqueous potassium persulfate (0.6%, 50 mL) was added over a 5 min period.
  • Reactor pressure was maintained at 300 psi until 220 g of VF2 had been fed after initiator addition. Agitation was stopped and the reactor was cooled and vented. The resulting milky dispersion was frozen and thawed to coagulate the product which was filtered through Nylon cloth and washed with water repeatedly to remove surfactant.
  • EXAMPLE 4 In the present example, a small molecule reaction is presented as an analog to the formation of a cyano-substituted methide ionomer.
  • VF2/PSEPVE copolymer is converted to the lithium dicyanomethide derivative.
  • a 300 mL flask was charged with
  • EXAMPLE 6 1.0 gram of the lithium-form polymer of Example 3 was mixed with 2.5 grams of propylene carbonate (PC, E.M. Industries, Selectipur) on a hot plate at 100°C in a nitrogen-purged Vacuum Atmospheres glove box until a clear deep red gel resulted. This gel was melt pressed at 120°C with 3 klbs pressure using a Carver Hydraulic Unit Model #3912 press inside the glove box to give a 4.0 mil thick clear pink film. A 1.0 by 1.5 cm 2 section of this film was cut with a razor and assembled into a four-point-probe conductivity cell. Ionic conductivity was determined according to the method of Doyle et al, WO98/20573.
  • the conductivity of the film under ambient conditions was equal to 7.75xl0 -4 S/cm.
  • a second sample of this membrane was immersed into an excess of a 1 :1 by volume mixture of ethylene carbonate (EC, E.M. Industries, Selectipur) and gamma-butyrolactone (GBL, E.M. Industries, Selectipur) for 30 minutes at room temperature. At the end of this period, the membrane sample was removed and blotted dry and its weight and ionic conductivity were measured. The film was highly swollen but still strong and elastic when fully imbibed with solvent. Weight uptake of the film was 766% and the ionic conductivity was 1.67x10-3 s/cm.
  • Acetonitrile purchased from EM Science (Gibbstown, New Jersey) was refluxed over P 2 O5 for at least 12 h, collected under dry nitrogen; it was stored over activated 4 A
  • Potassium fluoride was purchased from Aldrich Chemical Company; melted in a Pt dish with a torch and placed immediately in the chamber of the dry box; ground and stored thereafter inside the dry box.
  • CF 3 SO 2 NH 2 purchased from TCI America (Portland, Oregon), was sublimed twice at 10 * " 3 Torr while using an oil bath temperature of 60°C and a water cooled sublimation finger.
  • Zn dust was purchased from Aldrich ( ⁇ 10 microns, 98+%) and activated with HC1 according to standard procedures.
  • PSEPVE was synthesized according to the teachings of U.S. 5,463,005 (1995). It was distilled under vacuum. I(CF 2 ) I, available from TCI, Portland, Oregon, was converted to NaSO 2 (CF 2 ) 4 SO Na followed by the reaction with chlorine to obtain ClSO 2 (CF 2 ) 4 SO 2 Cl according to the teachings of Qiu and Burton (J. Fluorine Chem., 60 (1993) 93-100). C 4 F 9 I, available from TCI, was converted to, C4F 9 SO 2 Cl according to the teachings of Hu and DesMarteau (Inorg.Chem. 32 (1993) 5007. EXAMPLE 7
  • EXAMPLE 10 30.0 g (94.2 mmol) of C 4 F 9 SO 2 Cl were placed in a 250 ml round bottom flask. 125 ml of anhydrous acetonitrile and 55.1 g (948 mmol) of fused KF was added. The reaction mixture was stirred at room temperature for 42 h. All volatiles were removed and the residue was heated at 80° C for 18h. 78.6 g (4.62 mol) anhydrous ammonia was added to the collected volatile fraction at -196°C. The reaction mixture was warmed to room temperature under an inert argon atmosphere allowing excess ammonia to evaporate overnight. All volatiles were removed under vacuum. The residue was heated to 45°C for 5h under vacuum.
  • the reaction mixture was filtered through a paper filter to give the product CF 3 SO 2 N(K)SO 2 (CF 2 ) 4 SO 2 N(K)SO 2 CF 2 CF 2 OCF(CF 3 )CF 2 OCFBrCF 2 Br.
  • the product can readily be debrominated as in Example 7.
  • EXAMPLE 12 According to the method of Example 1, a 1 liter autoclave was charged with a solution of 12.8 g (22.0 mmol) of the ionic lithium composition of Example 9 in 400 g deionized water. The solution was cooled and degassed and the reactor was charged withl5 g (0.234 mol) of vinylidene fluoride. The solution was brought to 60°C (pressure in reactor: 116.1 psig; rpm: 750) after which 20 ml of a solution of 0.201 g potassium persulfate in 50 g deionized water was added over a period of 10 min. The reactor pressure diminished to 0 psig after 16h. The copolymer was isolated by lyophilization.
  • EXAMPLE 13 0.865 g of the ionomer of Example 12 and 70 ml acetone was stirred for 12 h at room temperature and then poured into a 10 cm PFA dish. The solvent was allowed to evaporate slowly to provide a copolymer film which was peeled from the dish. The membrane was heated in a vacuum oven at 100°C for 12 hours after which it became somewhat brittle. Film thickness was 120 micrometers.
  • the VF2-copolymer was isolated by lyophilization. The material was dried at 110°C for 22 hr to afford the yield was 40.7 g of ionomer containing 4.7 mol-% of the lithium imide
  • Thickness 100 °C for 12 h. Thickness wasl90 micrometers.
  • a cathode To form a cathode, the following materials were weighed and hand-mixed in a 50-ml glass jar inside a glove box under a dry nitrogen atmosphere: 0.625 grams (2.5 wt%) of Kynar Flex ® 2801 polyvinylidene fluoride, from Atochem. 1.75 grams (7.0 wt%) of the ionomer of Example 14 15.5 grams (62 wt%) of LiCoO , from EM Industries. 1.625 grams (6.5 wt%) of Super P carbon black from MMM Carbon.
  • Rotor speed 192 rpm.
  • the thus melt-compounded material was extruded through a circular die with a diameter of 0.32 cm, and was collected in a glass jar purged with dry nitrogen.
  • a 1.0 gram quantity of the extrudate was was melt-pressed between the platens of the Carver press at 110°C and 20 klbs ram force inside a nitrogen- purged glove box, followed by cooling and release of pressure thereby forming a film of 5 mil thickness.
  • a 12 mm diameter circular specimen was punched out of the film so formed.
  • the separator and cathode films prepared as hereinabove described were each exposed for 2 hours to an electrolyte solution composed of 1.0 M LiPFg in 1 : 1 EC/GBL by immersion in 2-4 ml of solution in a sealed glass vial for two hours.
  • the so-treated cathode and separator film were assembled into size 2325 coin cells with 3 layers of 4 mil thick lithium metal as the negative electrode.
  • the coin cell was cycled at the C/5 rate for both charge and discharge at room temperature between the voltage limits of 4.2 V and 2.8 V.
  • Capacity during the first charge for the LiCoO 2 cathode was 157.2 mAh g, while capacity for the first discharge was 149.7 mAh g, giving a reversibility of 95.2%.
  • Capacity on the tenth discharge was 147.1 mAh/g and the coin cell achieved nearly 100 cycles to 80% of its initial capacity.

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Abstract

L'invention concerne des ionomères sensiblement fluorés mais non perfluorés, ainsi que des monomères ioniques et nonioniques apparentés, les groupes latéraux desdits ionomères contenant des dérivés de fluorosulfonylméthide ou de fluorosulfonylimide. L'invention concerne également les sels métalliques monovalents de ces ionomères, ainsi que l'utilisation de ces derniers dans des applications électrochimiques, par exemple des batteries, des piles à combustible, des cellules électrolytiques, des membranes échangeuses d'ions, des capteurs, des fenêtres électrochromiques, des condensateurs électrochimiques, et des électrodes modifiées.
PCT/US1999/004574 1998-03-03 1999-03-03 Ionomeres sensiblement fluores Ceased WO1999045048A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DE69904919T DE69904919T2 (de) 1998-03-03 1999-03-03 Im wesentlichen fluorierte ionomere
CA002321695A CA2321695A1 (fr) 1998-03-03 1999-03-03 Ionomeres sensiblement fluores
EP99911046A EP1060200B1 (fr) 1998-03-03 1999-03-03 Ionomeres sensiblement fluores
AT99911046T ATE231169T1 (de) 1998-03-03 1999-03-03 Im wesentlichen fluorierte ionomere
IL13793299A IL137932A0 (en) 1998-03-03 1999-03-03 Substantially fluorinated ionomers
AU29781/99A AU2978199A (en) 1998-03-03 1999-03-03 Substantially fluorinated ionomers
JP2000534589A JP4417554B2 (ja) 1998-03-03 1999-03-03 相当にフッ素化されたイオノマー
KR1020007009720A KR20010041541A (ko) 1998-03-03 1999-03-03 실질적으로 플루오르화된 이오노머
NO20004334A NO20004334L (no) 1998-03-03 2000-08-31 Idet vesentlige fluorerte ionomerer

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US7657898P 1998-03-03 1998-03-03
US60/076,578 1998-03-03

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CN (1) CN1292005A (fr)
AT (1) ATE231169T1 (fr)
AU (1) AU2978199A (fr)
CA (1) CA2321695A1 (fr)
DE (1) DE69904919T2 (fr)
IL (1) IL137932A0 (fr)
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WO2000052085A1 (fr) * 1999-03-03 2000-09-08 E.I. Du Pont De Nemours And Company Procede de fusion continue permettant de fabriquer des articles conducteurs par migration des ions
WO2000077057A3 (fr) * 1999-06-16 2001-03-29 Du Pont Polymeres ioniques fluores
WO2001040174A1 (fr) * 1999-12-02 2001-06-07 E.I. Du Pont De Nemours And Company Procede de preparation d'imides a partir de fluorures de sulfonyle
WO2001047872A1 (fr) * 1999-12-23 2001-07-05 E.I. Dupont De Nemours And Company Methode de preparation de monomere d'imide de fluorosulfonyle
WO2001049757A1 (fr) * 1999-12-29 2001-07-12 HYDRO-QUéBEC Elastomeres fluorosulfones a faible tg a base de fluorure de vinylidene
US6395838B1 (en) 2000-01-19 2002-05-28 E. I. Du Pont De Nemours And Company Process for making graft copolymers
WO2002062749A1 (fr) * 2001-02-01 2002-08-15 Asahi Kasei Kabushiki Kaisha Monomere d'ether perfluorovinylique ayant un groupe sulfonamide
JP2002298852A (ja) * 2001-03-22 2002-10-11 Ilion Technology Corp アイオノマーバインダーを有する電気化学セルおよびこれに関連した製造方法
US6777515B2 (en) 2001-07-13 2004-08-17 I. Du Pont De Nemours And Company Functional fluorine-containing polymers and ionomers derived therefrom
US6838023B2 (en) 2000-08-04 2005-01-04 E. I. Du Pont De Nemours And Company Trivanadium oxide hydrate compositions
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WO2011051168A1 (fr) * 2009-10-29 2011-05-05 Solvay Solexis S.P.A. Procédé d'isolement de polymères de fluorure de sulfonyle et polymères obtenus par ce procédé
US8491819B2 (en) 2006-12-29 2013-07-23 E I Du Pont De Nemours And Company High work-function and high conductivity compositions of electrically conducting polymers
US8765022B2 (en) 2004-03-17 2014-07-01 E I Du Pont De Nemours And Company Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
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WO2000052085A1 (fr) * 1999-03-03 2000-09-08 E.I. Du Pont De Nemours And Company Procede de fusion continue permettant de fabriquer des articles conducteurs par migration des ions
WO2000077057A3 (fr) * 1999-06-16 2001-03-29 Du Pont Polymeres ioniques fluores
WO2001040174A1 (fr) * 1999-12-02 2001-06-07 E.I. Du Pont De Nemours And Company Procede de preparation d'imides a partir de fluorures de sulfonyle
US6759477B2 (en) 1999-12-02 2004-07-06 E. I. Du Pont De Nemours And Company Method for preparing imides from sulfonyl fluorides
WO2001047872A1 (fr) * 1999-12-23 2001-07-05 E.I. Dupont De Nemours And Company Methode de preparation de monomere d'imide de fluorosulfonyle
WO2001049757A1 (fr) * 1999-12-29 2001-07-12 HYDRO-QUéBEC Elastomeres fluorosulfones a faible tg a base de fluorure de vinylidene
US6642319B2 (en) 2000-01-19 2003-11-04 E. I. Du Pont De Nemours And Company Process for making graft copolymers
US6395838B1 (en) 2000-01-19 2002-05-28 E. I. Du Pont De Nemours And Company Process for making graft copolymers
CN100369298C (zh) * 2000-02-25 2008-02-13 日本电气株式会社 二次电池
US6838023B2 (en) 2000-08-04 2005-01-04 E. I. Du Pont De Nemours And Company Trivanadium oxide hydrate compositions
WO2002062749A1 (fr) * 2001-02-01 2002-08-15 Asahi Kasei Kabushiki Kaisha Monomere d'ether perfluorovinylique ayant un groupe sulfonamide
CN1318398C (zh) * 2001-02-01 2007-05-30 旭化成株式会社 具有磺酰胺基的全氟乙烯基醚单体
JP2002298852A (ja) * 2001-03-22 2002-10-11 Ilion Technology Corp アイオノマーバインダーを有する電気化学セルおよびこれに関連した製造方法
US6777515B2 (en) 2001-07-13 2004-08-17 I. Du Pont De Nemours And Company Functional fluorine-containing polymers and ionomers derived therefrom
US8765022B2 (en) 2004-03-17 2014-07-01 E I Du Pont De Nemours And Company Water dispersible polypyrroles made with polymeric acid colloids for electronics applications
US8491819B2 (en) 2006-12-29 2013-07-23 E I Du Pont De Nemours And Company High work-function and high conductivity compositions of electrically conducting polymers
US8822588B2 (en) 2008-06-12 2014-09-02 Central Glass Company, Limited Fluorine-containing polymer and anti-static agent wherein same is used
WO2011051168A1 (fr) * 2009-10-29 2011-05-05 Solvay Solexis S.P.A. Procédé d'isolement de polymères de fluorure de sulfonyle et polymères obtenus par ce procédé

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IL137932A0 (en) 2001-10-31
CA2321695A1 (fr) 1999-09-10
EP1060200B1 (fr) 2003-01-15
AU2978199A (en) 1999-09-20
EP1060200A1 (fr) 2000-12-20
CN1292005A (zh) 2001-04-18
NO20004334D0 (no) 2000-08-31
KR20010041541A (ko) 2001-05-25
US6667377B2 (en) 2003-12-23
ATE231169T1 (de) 2003-02-15
DE69904919D1 (de) 2003-02-20
NO20004334L (no) 2000-10-30
JP2002505356A (ja) 2002-02-19
DE69904919T2 (de) 2003-11-13
JP4417554B2 (ja) 2010-02-17
US20020045713A1 (en) 2002-04-18

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